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Simultaneous Formation of FeOx Electrocatalyst Coating within Hematite Photoanodes for Solar Water Splitting

  • Dominic Walsh*
    Dominic Walsh
    Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
    *E-mail: [email protected]
  • Jifang Zhang
    Jifang Zhang
    Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
    More by Jifang Zhang
  • Miriam Regue
    Miriam Regue
    Centre for Sustainable Chemical Technologies, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
    Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
    More by Miriam Regue
  • Ruchi Dassanayake
    Ruchi Dassanayake
    Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
  • , and 
  • Salvador Eslava*
    Salvador Eslava
    Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
    *E-mail: [email protected]
Cite this: ACS Appl. Energy Mater. 2019, 2, 3, 2043–2052
Publication Date (Web):February 26, 2019
https://doi.org/10.1021/acsaem.8b02113
Copyright © 2019 American Chemical Society
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Abstract

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Depositing an oxygen evolution electrocatalyst on the intricate pores of semiconductor light-absorbing layers of photoanodes for photoelectrochemical solar water splitting is an efficient way to improve their performance, but it adds extra costs and difficulties. In this work, we present a synthesis of hematite (α-Fe2O3) photoanodes with a self-derived conductive amorphous FeOx electrocatalyst coating. Hematite-FeOx photoanodes were prepared via FeOOH precursors modified with low levels of lactic acid additive. In the absence of lactic acid, FeOOH consisted of lepidocrocite nanorods that resulted in α-Fe2O3 particulate photoanodes with sharp crystal edges upon doctor blading and calcination. Lactic acid addition, however, resulted in goethite and amorphous FeOOH that formed α-Fe2O3 particulate photoanodes coated by a thin conductive amorphous FeOx layer. Electron microscopy studies revealed that the thickness of this layer was controlled with the addition of lactic acid in the preparation. Photoelectrochemical characterization including Tafel plots, impedance spectroscopy, and hole scavenger measurements confirmed that the FeOx layer behaved as an FeOOH electrocatalyst enhancing charge transfer efficiency and minimizing electron–hole surface recombination. Such coating and approach increased the electrochemically active surface area and amount of surface states. Photocurrent increased from 0.32 to 1.39 mA cm–2 at 1.23 VRHE under simulated sunlight, remarkable results for an auto-co-catalyzed and simple solution-process deposition.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.8b02113.

  • Raman spectroscopy, crystal structure of hematite and (110) plane, SEM cross-sections of hematite/FTO slides, TEM of hematite/FeOx, EDXS elemental mapping, XPS, cyclic voltammetry curves, repeat photocurrent measurements, photoanode sample stability measurement, UV–vis spectroscopy and Tauc plots, and Faradaic efficiency measurements (PDF)

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Cited By


This article is cited by 10 publications.

  1. Shufeng Zhang, Pengpeng Shangguan, Shaoping Tong, Zhao Zhang, Wenhua Leng. Enhanced Photoelectrochemical Oxidation of Water over Ti-Doped α-Fe2O3 Electrodes by Surface Electrodeposition InOOH. The Journal of Physical Chemistry C 2019, 123 (40) , 24352-24361. https://doi.org/10.1021/acs.jpcc.9b05419
  2. Yongpeng Liu, Florian Le Formal, Florent Boudoire, Néstor Guijarro. Hematite Photoanodes for Solar Water Splitting: A Detailed Spectroelectrochemical Analysis on the pH-Dependent Performance. ACS Applied Energy Materials 2019, 2 (9) , 6825-6833. https://doi.org/10.1021/acsaem.9b01261
  3. Yifan Wang, Xiaohu Cao, Qiyu Hu, Xiangming Liang, Tian Tian, Junqi Lin, Meie Yue, Yong Ding. FeOx Derived from an Iron-Containing Polyoxometalate Boosting the Photocatalytic Water Oxidation Activity of Ti3+-Doped TiO2. ACS Applied Materials & Interfaces 2019, 11 (26) , 23135-23143. https://doi.org/10.1021/acsami.9b03714
  4. Bofan Zhang, Irfan Khan, Yasuhito Nagase, Ahmed S. Ali, Stjepko Krehula, Mira Ristić, Svetozar Musić, Shiro Kubuki. Highly covalent FeIII–O bonding in photo-Fenton active Sn-doped goethite nanoparticles. Materials Chemistry and Physics 2022, 287 , 126247. https://doi.org/10.1016/j.matchemphys.2022.126247
  5. Zhenhua Pan, Rito Yanagi, Tomohiro Higashi, Yuriy Pihosh, Shu Hu, Kenji Katayama. Hematite photoanodes prepared by particle transfer for photoelectrochemical water splitting. Sustainable Energy & Fuels 2022, 6 (8) , 2067-2074. https://doi.org/10.1039/D2SE00145D
  6. I. Khan, Ahmad S. Ali. Characterization of Iron Oxide and Doped Iron-Oxide Nanocomposites for Photocatalytic Degradation of Organic Compounds. 2022,,, 1-39. https://doi.org/10.1007/978-3-030-34007-0_53-1
  7. Behrooz Eftekharinia, Nader Sobhkhiz Vayghan, Ali Esfandiar, Ali Dabirian. Effect of film morphology on water oxidation enhancement in NiFeCo modified hematite photoanodes. Surface and Coatings Technology 2021, 421 , 127362. https://doi.org/10.1016/j.surfcoat.2021.127362
  8. Da Hye Hong, D. Amaranatha Reddy, K. Arun Joshi Reddy, Madhusudana Gopannagari, D. Praveen Kumar, Tae Kyu Kim. Synergetic catalytic behavior of dual metal-organic framework coated hematite photoanode for photoelectrochemical water splitting performance. Journal of Catalysis 2020, 391 , 471-479. https://doi.org/10.1016/j.jcat.2020.09.014
  9. Shufeng Zhang, Zhao Zhang, Wenhua Leng. Understanding the enhanced photoelectrochemical water oxidation over Ti-doped α-Fe 2 O 3 electrodes by electrochemical reduction pretreatment. Physical Chemistry Chemical Physics 2020, 22 (15) , 7835-7843. https://doi.org/10.1039/C9CP06138J
  10. Alexander N. Bondarchuk, Iván Corrales-Mendoza, Sergio A. Tomás, Frank Marken. A hematite photoelectrode grown on porous and conductive SnO2 ceramics for solar-driven water splitting. International Journal of Hydrogen Energy 2019, 44 (36) , 19667-19675. https://doi.org/10.1016/j.ijhydene.2019.06.055

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